Synthesis of 4-aziridino [C60]fullerene-1,8-naphthalimide(C 60-NI dyads) and their photophysical properties

Article abstract of DOI:10.1016/j.tet.2010.05.019

A series of 4-aziridino[C₆₀]fullerene-1,8-naphthalimide (C ₆₀-NI) dyads 4 ([6,6]-closed ring) were synthesized as the only addition product from the reaction of C₆₀ with the corresponding azide compounds 3 under microwave

Full text of DOI:10.1016/j.tet.2010.05.019

Tetrahedron 66 (2010) 5467e5471
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of 4-aziridino[C60]fullerene-1,8-naphthalimide (C60-NI dyads)
and their photophysical properties
,
b
,
b
Fengrui Liu a, Weiqiong Du a, Qin Liang a, Yuqin Wang a, Jianmin Zhang a , Jingwei Zhao ,
*
,
Shizheng Zhu b
*
a Department of Chemistry, School of Science, Shanghai University, No. 99, Shangda Road, Shanghai 200444, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of 4-aziridino[C60]fullerene-1,8-naphthalimide (C60-NI) dyads 4 ([6,6]-closed ring) were syn-
thesized as the only addition product from the reaction of C60 with the corresponding azide compounds
3 under microwave irradiation in good yield. A quenching of fluorescence was shown in dyads 4, and this
decay was evidenced to be an intramolecular process.
Received 10 March 2010
Received in revised form 6 May 2010
Accepted 7 May 2010
Available online 12 May 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
C60
1,8-Naphthalimide
Azide
Aziridinofullerene
Flourescent switch
1. Introduction
herein we report an efficient synthetic route to NI-C60 dyads (only
closed [6,6]-bridged aziridinofullerene) and their spectroscopic
properties.
[C60]Fullerene1,2 is
a
redox-active chromophore, which,
according to theoretical calculations, exhibits a LUMO (t1u) com-
paratively low in energy and is triply degenerate. Therefore, C60
behaves like an electronegative molecule, which could reversibly
accept up to six electrons in solution.3 And also, the cyclic vol-
tammetry and the electron affinity measured for [C60]fullerene
clearly confirm that it is a moderate electron acceptor comparable
to other organic molecules such as benzo- and naphthoquinones.4,5
Consequently, in the design of the new functional materials based
on the electron acceptoredonor systems, [C60]fullerene, as the
electron-acceptor, has dominated the field compared to any other
electron-acceptor.
In recent years, the perylene-3,4:9,10-bis(dicarboximide) (PDI)
chromophore has received an increasing interest. It was attached to
fullerene C60 with the aim of reaching new light-harvesting sys-
tems.6,7 An efficient intramolecular energy transfer from the PDI
toward fullerene C60 was evidenced in these dyads.8,9 To our
knowledge, the 1,8-naphthalimide (NI) chromophore has never
been attached to an acceptor such as [C60]fullerene, especially
through the synthesis of fulleroaziridines.10 As a part of our con-
tinuous study on the chemical transformation of C60-fullerene,
2. Results and discussion
2.1. Synthesis
The strategy for the synthesis of 4-aziridino[C60]fullerene-1,8-
naphthalimide 4 (NI-C60 dyads) used the starting material 4-
bromo-naphthalene anhydride 1 (Scheme 1). 4-Bromo-1,8-naph-
thalimide 2 was synthesized by treating 1 with aryl or alkyl amines
in refluxing ethanol,11 then the imides were heated with NaN3 in
DMF at 100 ꢀC for 6 h to afford 4-azide-1,8-naphthalimide 312 in
moderate yields. Thermal reaction of C60 (0.1 mmol) with two equal
molar 3b was first carried out in chlorobenzene (15 mL) at 130 ꢀC.
After stirring the reaction mixture for 6 h, the reaction was finished,
chromatography on silica gel using toluene as eluent gave
unconvered C60 (30 mg) and the addition product 4b (20 mg, 29%).
When the molar ratio of 3b to C60 was increased from 2:1 to 3:1 and
then to 4:1, the yield of 4b increased to 40% and 42%, respectively. In
order to try higher reaction temperature, o-dichlorobenzene (o-
DCB) was used as solvent. Under 160 ꢀC, C60 was stirred with the
excess azide 3b (3:1) for 6 h, and the yield of 4b was increased up to
56%. Further increasing the reaction temperature (180 ꢀC) leads to
the decrease of the yield of 4b clearly (30%).
* Corresponding authors. E-mail address: zhusz@mail.sioc.ac.cn (S. Zhu).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.05.019

5468
F. Liu et al. / Tetrahedron 66 (2010) 5467e5471
Scheme 1. Preparation of the dyads 4ae4f.
Under microwave irradiation (120 ꢀC, 700 W), the reaction of
C60 with three equal molar 3b in o-DCB was finished in 3 min and
afforded addition product 4b in high yield (73%). Longer irradiating
time decreased the yield of 4b (Table 1, Entry 10).
[6,6]-irradiated azafulleroid products (NI-C60) 4a and 4ce4f in
70e73% yields (Table 2).
Table 2
Preparation of NI-C60 dyads 4 under microwave irradiation conditiona
Entry
Reactant
Product
Yieldb (%)
Table 1
Reaction results of C60 with 3b under different reaction conditions
1
2
3
4
5
6
3a
3b
3c
3d
3e
3f
4a
4b
4c
4d
4e
4f
70
73
72
71
71
72
Entry
Mole ratioa
Methodb
130 ꢀ
Solvent
Time
Yieldc (%)
1
2
3
4
3
3
2
3
4
3
C
Chlorobenzene
Chlorobenzene
Chlorobenzene
o-DCB
6 h
29
40
42
56
30
53
73
74
58
2
3
4
5
6
7
8
10
130 ꢀC
130 ꢀC
160 ꢀC
180 ꢀC
MW
MW
MW
MW
6 h
6 h
6 h
6 h
3 min
3 min
3 min
5 min
a
Ratio of 3b/C60¼3:1 irradiated under microwave (120 ꢀC) for 3 min.
o-DCB
o-DCB
o-DCB
o-DCB
b
Isolated yield based on the reacted C60
.
2.2. Theoretical calculations
o-DCB
a
Ratio of 3b/C60
.
Quantum chemical calculations on the two dyads 4a, 4f have
been conducted to get further insights of molecular structure.
Geometrical optimization was performed with semiempirical
methods using PM3 parametrization with Hyperchem 7.5. The alkyl
group is found to be the tail of the planar naphthalimide core, but
the phenyl group is nearly perpendicular to the planar naph-
thalimide core, thus minimizing steric hindrance between phenyl
group and the imide functionality (Fig. 1). On the opposite part of
the system, the plane of the phenyl spacer is oriented out of the
naphthalimide plane.
b
Heated or irradiated under microwave (120 ꢀC).
c
Isolated yield based on the reacted C60
.
The structure of 4b was fully identified by standard spectro-
scopic methods. The TOF mass spectrum of 4b shows its molecular
ion peak at m/z¼1098 and the base peak at 720. The 13C NMR shows
only 17 peaks for C60 skeleton [16 between 141.0 and 146.5 ppm
and 1 peak for the sp3 hybridized carbon at 82.6 ppm]. This in-
dicates for compound 4b C2v-symmetry with a [6,6] junction on the
fullerene core. The two peaks at 163.7, 163.3 ppm are attributed to
the two carbonyl carbon atoms for C]O, and 10 peaks at
119.9e134.9 ppm for the naphthalimide or aromatic carbon atoms,
furthermore the remaining 12 peaks at 14.5e40.6 belong to the
alkyl group (C12H25e). The UV spectrum of dyad 4b exhibits the
fullerene bands in the region of around 260 nm, 330 nm, and
420 nm (the typical bands of [6,6]-closed aziridinofullerene
derivative) and the bands of the NI moiety around 375 nm (see
Fig. 2a).
Generally, the reaction of C60 with azide compounds should give
both [5 6]-bridged azafulleroid and [6,6]-closed ring azir-
idinofullerene products. In this case, however, only [6,6]-closed
ring product was formed. In our previous study, we also found that
the perfluoroalkanesulfonyl azides RfSO2N3 reacted with C60 giving
only [5,6]-open ring products.13 Therefore, it was believed that the
structure of NI gives rise to this unusual consequence.
Figure 1. Optimized geometries of C60-NI 4a (left), 4f (right).
2.3. UV spectra
Under the optimum reaction conditions (Table 1, entry 7), other
4-azide-1,8-naphthalimides (3a, 3ce3f) added to C60 all affording
Compounds 4 exhibit a typical UVevis absorption profile of
NIefullerene adducts with four distinct broadband, at 240e430 nm

F. Liu et al. / Tetrahedron 66 (2010) 5467e5471
5469
region: a sharp absorption band characteristic of fullerene adducts
at 260 nm, as well as the comparably intense band around 330 nm,
the typical band of [6,6]-closed aziridinofullerene derivative
around 420 nm, and the longest wavelength absorption band at
360e400 nm corresponding to the NI moiety (Fig. 2a). The ab-
sorption at 360e400 nm of the dyad 4d is much stronger than 4b,
which indicates that the substitution (R) on the NI moiety (aromatic
or alkyl group) seems to have an obvious influence on the ab-
sorption feature corresponding to the NI moiety.
from the N-alkyl dyads to N-aryl dyads, the quenching decreases,
suggesting that as the substitution of NI moiety, the aryl is better
than the alkyl in restarting fluorescence (Table 3). Second, the
quenching of 4de4f correlates well with the electron-withdrawing
strength of the substituent of NI moiety (Table 3).
When triethylamine (TEA) was added to the solution of 4d in
chloroform, the fluorescence quenching was largely affected. The
quenching increased largely as TEA was added from 1% to 10%
(Fig. 2d). However, the quenching remained almost unchanged
Figure 2. a. UVevis spectra of 4b and 4d, c<10ꢁ4 mol/L, in CH2Cl2. b. The fluorescence emission spectra of 2d, 3d. and 4d, c¼10ꢁ4 mol/L in CHCl3, excited in 434 nm. c. The
fluorescence emissions spectra of 4a and 4d, c¼10ꢁ4 mol/L in CHCl3, excited in 434 nm. d. The fluorescence emission spectra of 4d when Et3N and HOAc were added (c¼10ꢁ4 mol/L
in CHCl3).
2.4. Photophysical properties
when HOAc was added from 1% to 10% (Fig. 2d). Because of the ‘on
and off’ property when added TEA, the dyad 4d would be consid-
ered as a potential candidate of the fluorescent switch.14
The dyad’s fluorescence is subjected to a strong quenching rel-
ative to the corresponding reference 4-azide-1,8-naphthalimide
derivative 3d (Fig. 2b). Figure 2b also shows the emission spectra of
4d and 2d, measured with excitation in the region of the NI chro-
mophore in CHCl3. Compared to the strong quenching of 2d, the
Table 3
Selected photophysical data of dyads 4 at 298 K
Dyads
Intensity
Quenchinga
lmax (nm)
Solvent
dyad 4d’s quenching is weaker. This quenching suggests that [C60
]
4a
4b
4c
4d
4d
4e
4f
1.757
0.798
0.945
35.833
33.600
22.500
1.878
0.951
0.978
0.974
0
488
496
464
476
499
498
502
Toluene
Toluene
Toluene
Toluene
CHCl3
fullerene imido is better than the bromo in restarting fluorescence.
The decay process must be intramolecular. This is evidenced by the
experiment that the fluorescence of 3d was not affected using
a stoichiometric mixture of 3d and C60 in concentration similar to
the case of dyad 4d. This intramolecular decay of NI-C60 has two
possibilities. One is between the NI moiety and the fullerene. Such
decay was also observed by the experiment that, when 4d is com-
pared with 3d, the emission from the NI moiety is markedly de-
pressed (Fig. 2b). The other is between the Ar component and the NI
component. This is evidenced by the observation that 4d also shows
a different emission from the NI moiety as compared to 4a (Fig. 2c).
A closer inspection of the fluorescence quenching, reveals two
trends in regarding the magnitude of fluorescence quenching. First,
0
0.330
0.945
CHCl3
CHCl3
a
Quenching¼(Intensity4dꢁIntensity)/Intensity4d
.
3. Conclusion
In conclusion, the synthesis and spectroscopic studies of the
fulleroaziridines are described. 4-Aziridino[C60]fullerene-1,8-
naphthalimide(C60-NI) dyads
4
([6,6]-closed ring) were

5470
F. Liu et al. / Tetrahedron 66 (2010) 5467e5471
synthesized through the aziridination reaction of C60 with the
corresponding azide compounds 3 under microwave irradiation in
high yield. It was found that this reaction only gave the [6,6]-closed
ring compound 4, without the [5,6]-open ring azafulleroid com-
pound. Maybe, this unusual consequence is caused by the specific
1H), 8.63 (d, J¼8.0 Hz, 1H), 8.50 (q, J¼8.5 Hz, 1H), 7.78 (q, J¼8.5 Hz,
1H), 7.51 (d, J¼8.0 Hz, 1H), 7.21 (d, J¼8.5 Hz, 18H), 7.04 (d, J¼8.5 Hz,
3H), 4.09 (q, J¼7.0 Hz, 2H), 1.45 (t, J¼7.0 Hz, 3H); EIMS: (m/z, %): 358
(Mþ, 63), 330 ([MꢁN2]þ, 100).
structure of NI.13 It was also clearly demonstrated that the NI
4.2.1.5. N-(4-Methylphenyl)-4-azido-1,8-naphthalimide (3e). Yield
15
moiety can act as a light-harvesting antenna for C60
.
In the
85%. IR (KBr, cmꢁ1):
n
3067, 3035, 2923, 2116, 1708, 1662, 1589,
emission spectrum of NI-C60 in CHCl3, the intramolecular decay
process is shown. When TEA was added, its fluorescence was
largely influenced, especially for the quenching magnitude. Con-
sequently, this dyad would be regarded as a potential candidate of
fluorescent switch.
1513, 1359, 782; 1H NMR (500 MHz, CDCl3):
d
(ppm) 8.68 (q, 1H,
J¼7.5 Hz), 8.63 (d, J¼8 Hz, 1H), 8.50 (q, J¼8.5 Hz, 1H), 7.78 (t,
J¼7.8 Hz, 1H), 7.50 (d, J¼8 Hz, 1H), 7.35 (d, J¼8 Hz, 2H), 7.19 (t,
J¼8.5 Hz, 2H); 2.44 (s, 3H); EIMS: (m/z, %): 328 (Mþ, 30), 300
([MꢁN2]þ, 100).
4. Experimental section
4.1. General remarks
4.2.1.6. N-Phenyl-4-azido-1,8-naphthalimide (3f). Yield 85%. IR
(KBr, cmꢁ1):
n
3064, 2120, 1710, 1662, 1586, 1509, 1360, 782; 1H
NMR (500 MHz, CDCl3):
d
(ppm) 8.67 (d, 1H, J¼7.0 Hz), 8.62 (d,
J¼8.0 Hz, 1H), 8.50 (d, J¼8.5 Hz, 1H), 7.78 (t, J¼7.5 Hz, 1H), 7.55 (d,
J¼7.0 Hz, 2H), 7.50 (d, J¼7.5 Hz, 2H), 7.32 (d, J¼7.0 Hz, 2H); EIMS:
(m/z, %): 314 (Mþ, 18), 286 ([MꢁN2]þ, 100).
C60 was purchased from Wuhan University and in 99% purity. All
reactions for the synthesis of 4 were performed in a microwave
oven, under nitrogen atmosphere. o-Dichlorobenzene, carbon
disulfide, toluene, and ethyl acetate were used in AR quality. 1H, and
13C NMR spectra were recorded at 500 MHz and 125 MHz,
respectively, with chemical shift values being reported in parts per
million relative to chloroform for 1H NMR and 13C NMR. Infrared
spectra were obtained using an FT-IR spectrometer. Mass spectra
were recorded using an ES or EI ion source. Ultraviolet spectra were
performed with a UV spectrophotometer. Fluorescent spectra were
performed with a spectrofluorometer.
4.2.2. PreparationofN-dodecyl-4-aziridinofullerene-1,8-naphthalimide
(4b) under microwave irradiation condition. N-Dodecyl-4-azido-1,8-
naphthalimide 3b (122 mg, 0.3 mmol) and C60 (72 mg, 0.1 mmol)
were mixed in o-DCB (5 ml) in a 10 ml flask, then the mixture was
exposed to microwave irradiation at 120 ꢀC for 3 min under ni-
trogen atmosphere. The solvent was removed under reduced
pressure. The crude material was purified by flash column chro-
matography (using toluene as elute) affording 33 mg of un-
converted C60 (the first fraction) and 44 mg (73%) of the product
4b (the second fraction). Other dyads 4a and 4ce4f were prepared
similarly.
4.2. Synthesis
4.2.1. Preparation of N-dodecyl-4-azido-1,8-naphthalimide (3b). To
a suspension of 2b (443 mg, 10 mmol) in DMF (10 ml) was added
a suspension of sodium azide (65 mg, 10 mmol) in water (0.5 ml).
The mixture was heated to 100 ꢀC for 6 h and then poured into ice-
water (100 ml). The precipitate formed was filtered, washed with
water, and dried under vacuum. Compound 3b (345 mg, 85%) was
obtained as a yellow solid.
4.2.2.1. N-Octyl-4-aziridinofullerene-1,8-naphthalimide (4a). IR
(KBr, cmꢁ1):
n
2952, 2921, 2849, 1696, 1661, 1581, 1235, 1098, 1041,
779, 525; 1H NMR (500 MHz, CDCl3/CS2, 1:3):
d
(ppm) 9.31 (d,
J¼8.5 Hz, 1H), 8.68 (q, J¼7.5 Hz, 2H), 7.94 (q, J¼7.0 Hz, 2H), 4.16 (t,
J¼7.5 Hz, 2H), 1.74 (t, J¼7.5 Hz, 2H), 1.32e1.35 (m, 10H), 0.91 (t,
J¼5.8 Hz, 3H); ES-MS: (m/z, %): 1043 ([Mþ1]ꢁ, 8), 323
([MꢁC60þ1]ꢁ, 100).
4.2.1.1. N-Octyl-4-azido-1,8-naphthalimide (3a). Yield 86%. IR
(KBr, cmꢁ1):
n
3072, 2954, 2924, 2853, 2125, 1699, 1658, 1587, 1387,
4.2.2.2. N-Dodecyl-4-aziridinofullerene-1,8-naphthalimide(4b). IR
1353, 1290, 1234, 782; 1H NMR (500 MHz, CDCl3):
d
(ppm) 8.58 (d,
(KBr, cmꢁ1):
n
2960, 2920, 2849, 1696, 1661, 1582, 1261, 1096, 1022,
J¼7.0 Hz, 1H), 8.51 (d, J¼7.5 Hz, 1H), 8.37 (d, J¼8.5 Hz, 1H), 7.69 (d,
J¼7.8 Hz, 1H), 7.41 (d, J¼8.0 Hz, 1H), 4.12 (t, J¼7.8 Hz, 2H), 1.67e1.73
(m, 2H), 1.25e1.42 (m, 10H), 0.85 (t, J¼6.8 Hz, 3H); EIMS: (m/z, %):
350 (Mþ, 7), 322 ([MꢁN2]þ, 100).
802, 526; 1H NMR (500 MHz, CDCl3/CS2, 1:3):
d
(ppm) 9.30
(d, J¼8.5 Hz, 1H), 8.69 (d, J¼7.5 Hz, 2H), 7.90e7.94 (m, 2H), 4.16
(t, J¼7.0 Hz, 2H), 1.71e1.74 (m, 2H), 1.25e1.44 (m, 18H), 0.87
(t, J¼6.5 Hz, 3H); 13C NMR (125 MHz, CDCl3/CS2,1:3):
d (ppm) 163.74,
163.33, 146.52, 145.53, 145.42, 145.26, 145.14, 144.75, 144.47, 144.02,
143.81, 143.29, 143.25, 143.15, 143.01, 142.23, 141.29, 141.02,
134.95, 131.77, 131.57, 129.75, 128.48, 127.84, 127.33, 125.22, 124.09,
119.93, 82.56, 40.57, 32.24, 31.20, 30.00, 29.97, 29.92, 29.74,
29.70, 28.39, 27.45, 23.11,14.46; ES-MS: (m/z, %): 1098 ([M]ꢁ,12), 720
(Cꢁ60, 100).
4.2.1.2. N-Dodecyl-4-azido-1,8-naphthalimide (3b). Yield 85%. IR
(KBr, cmꢁ1):
n
2954, 2922, 2851, 2125, 1699, 1659, 1586, 1559, 1386,
1353, 1291, 1235, 781; 1H NMR (500 MHz, CDCl3):
d
(ppm) 8.65 (d,
J¼7.5 Hz, 1H), 8.60 (d, J¼8.0 Hz, 1H), 8.45 (d, J¼8.5 Hz, 1H), 7.76 (d,
J¼7.0 Hz, 1H), 7.49 (d, J¼8.0 Hz, 1H), 4.18 (t, J¼7.5 Hz, 2H), 1.72e1.77
(m, 2H), 1.27e1.45 (m, 18H), 0.90 (t, J¼6.5 Hz, 3H); EIMS: (m/z, %):
406 (Mþ, 2), 378 ([MꢁN2]þ, 100).
4.2.2.3. N-Hexadecyl-4-aziridinofullerene-1,8-naphthalimide
(4c). IR (KBr, cmꢁ1):
n
2963, 2920, 2850, 1661, 1531, 1261, 801,
4.2.1.3. N-Hexadecyl-4-azido-1,8-naphthalimide (3c). Yield 83%.
701, 520; 1H NMR (500 MHz, CDCl3/CS2, 1:3):
d
(ppm) 9.34 (d,
IR (KBr, cmꢁ1):
n
2959, 2920, 2850, 2125, 1699, 1660, 1586, 1353,
J¼8.5 Hz, 1H), 8.74 (d, J¼8.0 Hz, 2H), 7.94e7.98 (m, 2H), 4.21 (t,
J¼7.8 Hz, 2H), 1.75e1.77 (m, 2H), 1.44e1.48 (m, 2H), 1.36e1.38 (m,
2H), 1.25 (s, 22H), 0.88 (t, J¼6.8 Hz, 3H); 13C NMR (125 MHz,
781; 1H NMR (500 MHz, CDCl3):
d
(ppm) 8.64 (d, J¼7.0 Hz, 1H), 8.58
(d, J¼8.0 Hz, 1H), 8.43 (d, J¼8.0 Hz, 1H), 7.75 (d, J¼8.0 Hz, 1H), 7.47
(d, J¼8.0 Hz, 1H), 4.17 (t, J¼8.0 Hz, 2H), 1.70e1.76 (m, 2H), 1.26e1.43
(m, 26H), 0.89 (t, J¼7.0 Hz, 3H); EIMS: (m/z, %): 462 (Mþ, 11), 434
([MꢁN2]þ, 100).
CDCl3/CS2, 1:3):
d (ppm) 164.09, 163.68, 146.62, 145.50, 145.39,
145.21, 145.12, 144.72, 144.44, 143.99, 143.80, 143.25, 143.21,
142.98, 142.20, 142.18, 141.25, 140.96, 131.84, 131.62, 129.70,
128.60, 127.33, 125.20, 124.02, 123.95, 119.94, 118.94, 82.52, 44.11,
40.61, 32.03, 31.47, 30.20, 29.81, 29.80, 29.77, 29.75, 29.70, 29.53,
29.48, 28.28, 27.29, 22.82, 14.24; EIMS: (m/z, %): 1153 ([Mꢁ1]ꢁ,
20), 720 ([C60]ꢁ, 100).
4.2.1.4. N-(4-Ethoxyphenyl)-4-azido-1,8-naphthalimide (3d). Yield
83%. IR (KBr, cmꢁ1):
n
3067, 2984, 2913, 2873, 2126, 1707, 1665, 1585,
1512, 1361, 783; 1H NMR (500 MHz, CDCl3):
d
(ppm) 8.68 (q, J¼7.0 Hz,

F. Liu et al. / Tetrahedron 66 (2010) 5467e5471
5471
4.2.2.4. N-(4-Ethoxyphenyl)-4-aziridinofullerene-1,8-naph-
thalimide (4d). IR (KBr, cmꢁ1):
3068, 2963, 2921, 1708, 1666, 1586,
1511, 1361, 783, 531; 1H NMR (500 MHz, CDCl3):
(ppm) 8.69 (d,
J¼6.5 Hz, 1H), 8.67 (d, J¼7.0 Hz, 1H), 8.62 (t, J¼8.0 Hz, 1H), 7.78 (t,
J¼8.0 Hz, 1H), 7.51 (d, J¼8.0 Hz, 1H), 7.19 (d, J¼8.5 Hz, 2H), 7.03 (d,
J¼8.5 Hz, 2H), 4.10 (q, J¼7.0 Hz, 2H), 1.46 (t, J¼6.8 Hz, 3H); ES-MS:
(m/z, %): 1051 ([Mþ1]ꢁ, 20), 330 ([MꢁC60]ꢁ, 100).
Supplementary data
n
d
Supplementary data associated with this article can be found in
online version at doi:10.1016/j.tet.2010.05.019.
References and notes
1. Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985, 318,
162e163.
2. Kratschmer, W.; Lamb, L. D.; Fostiropoulus, K.; Huffman, D. R. Nature 1990, 347,
354e358.
3. (a) Arias, F.; Xie, Q.; Wu, Y.; Lu, Q.; Wilson, S. R.; Echegoyen, L. J. Am. Chem. Soc.
1994, 116, 6388e6394; (b) Allemand, P. M.; Koch, A.; Wudl, F.; Rubin, Y.; Die-
derich, F.; Alvarez, M. M.; Anz, S. J.; Whetten, R. L. J. Am. Chem. Soc. 1991, 113,
1050e1051; (c) Haufler, R. E.; Conceicao, J.; Chibante, L. P. F.; Chai, Y.; Byrne, N.
E.; Flanagan, S.; Haley, M. M.; O’Brien, S.; Pan, C.; Xiao, Z.; Billups, W. E.; Ciu-
folini, M. A.; Hauge, R. H.; Margrave, J. L.; Wilson, L. J.; Curl, R. F.; Smalley, R. E. J.
Phys. Chem. 1990, 94, 1050e1055.
4.2.2.5. N-(4-Methylphenyl)-4-aziridinofullerene-1,8-naph-
thalimide (4e). IR (KBr, cmꢁ1):
n
3067, 3031, 2958, 2922, 1710, 1663,
1586, 1512, 1361, 782, 520; 1H NMR (500 MHz, CDCl3/CS2, 1:3):
d
(ppm) 8.70 (d, J¼6.5 Hz, 1H), 8.64 (d, J¼8.0 Hz, 1H), 8.48 (d,
J¼8.0 Hz, 1H), 8.09 (d, J¼7.5 Hz, 1H), 7.90 (t, J¼8.0 Hz, 1H), 7.34 (d,
J¼7.0 Hz, 2H), 7.17 (d, J¼8.0 Hz, 2H), 2.46 (s, 3H); ES-MS: (m/z, %):
720 ([C60]ꢁ, 2), 299 ([MꢁC60ꢁ1]ꢁ, 100).
4. Saito, G.; Teramoto, T.; Otsuka, A.; Sugita, Y.; Ban, T.; Kusunoki, K. Synth. Met.
1994, 64, 359e368.
5. Wang, L. S.; Conceicao, J.; Jin, C.; Smalley, R. E. Chem. Phys. Lett. 1991, 182,
5e11.
4.2.2.6. N-Phenyl-4-aziridinofullerene-1,8-naphthalimide (4f). IR
(KBr, cmꢁ1):
n
3059, 2960, 2921, 1706, 1668, 1583, 1367, 692, 526;
1H NMR (500 MHz, CDCl3/CS2, 1:3):
d
(ppm) 8.72e8.74 (m,
6. Baffreau, J.; Perrin, L.; Leroy-Lhez, S.; Hudhomme, P. Tetrahedron Lett. 2005, 46,
4599e4603.
7. Wang, N.; Li, Y.; He, X.; Gan, H.; Li, Y.; Huang, C.; Xu, X.; Xiao, J.; Wang, S.; Liu,
H.; Zhu, D. Tetrahedron 2006, 62, 1216e1223.
2H),7.97e8.00 (m, 2H), 7.54 (t, J¼8.0 Hz, 2H), 7.47 (t, J¼8.5 Hz,
1H), 7.29 (d, J¼8.5 Hz, 2H), 7.20 (t, J¼7.5 Hz, 1H); 13C NMR
(125 MHz, CDCl3:CS2, 1:3):
d (ppm) 163.20, 163.17, 145.45, 145.33,
144.66, 144.36, 143.93, 143.93 143.64, 143.20, 143.16, 143.05,
142.93, 142.13, 141.22, 140.93 135.30, 132.03, 131.85, 130.48,
130.04, 129.17, 128.99, 128.71, 128.51, 127.57, 127.31, 125.29,
124.35, 124ꢁ.35, 123.95, 119.92, 82.47; EIMS: (m/z, %): 1006 (Mꢁ,
23), 720 (C60, 100).
8. Baffreau, J.; Leroy-Lhez, S.; Anh, N. V.; Williams, R. M.; Hudhomme, P. Chem.d
Eur. J. 2008, 14, 4974e4992.
9. (a) Tang, C. W. Appl. Phys. Lett. 1986, 48, 183e185; (b) Angadi, M. A.; Gosztola,
D.; Wasielewski, M. R. J. Appl. Phys. 1998, 83, 6187e6189; (c) Schmidt-Mende,
L.; Fechtenkotter, A.; Mullen, K.; Moons, E.; Friend, R. H.; MacKenzie, J. D.
Science 2001, 293, 1119e1122; (d) Breeze, A. J.; Salomon, A.; Ginley, D. S.;
Gregg, B. A.; Tillmann, H.; Horhold, H. H. Appl. Phys. Lett. 2002, 81,
3085e3087; (e) Li, J.; Kastler, M.; Pisula, W.; Robertson, J. W. F.; Wasserfallen,
D.; Grimsdale, A. C.; Wu, J.; Mullen, K. Adv. Funct. Mater. 2007, 17,
2528e2533; (f) Pandey, A. K.; Nunzi, J. M. Appl. Phys. Lett. 2007, 90, 263508/
1e263508/3.
4.2.3. Preparation
of
N-dodecyl-4-aziridinofullerene-1,8-naph-
thalimide (4b) under thermal reaction condition. A solution of C60
(101 mg, 0.14 mmol) and 3b (171 mg, 0.42 mmol) in 30 mL of o-DCB
was heated at 160 ꢀC for 6 h and the solvent was then evaporated
under reduced pressure. Similar work-up as the microwave irra-
diation reaction gave unconverted C60 (51 mg) and 4b (55 mg, 56%).
10. Martin, N.; Sanchez, L.; Illescas, B.; Perez, I. Chem. Rev. 1998, 98, 2527e2548.
11. Cao, H. S.; Chang, V.; Hernandez, R.; Heagy, M. D. J. Org. Chem. 2005, 70,
4929e4934.
12. Li, F.; Cui, J. N.; Guo, L. Y.; Qian, X. H.; Ren, W. M.; Wang, K. W.; Liu, F. Y. Bioorg.
Med. Chem. 2007, 15, 5114e5121.
13. Wu, R.; Lu, X. Y.; Zhang, Y.; Zhang, J. M.; Xiong, W. T.; Zhu, S. Z. Tetrahedron
2008, 64, 10694e10698.
14. Oike, T.; Kurata, T.; Takimiya, K.; Otsubo, T.; Aso, Y.; Zhang, H. M.; Araki, Y.; Ito,
O. J. Am. Chem. Soc. 2005, 127, 15372e15373.
15. Baffreau, J.; Ordronneau, L.; Leroy-Lhez, S.; Hudhomme, P. J. Org. Chem. 2008,
73, 6142e6147.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China NNSFC (No. 20972092).